EP0197578B1 - Mittel zum Behandeln von Textilien - Google Patents

Mittel zum Behandeln von Textilien Download PDF

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Publication number
EP0197578B1
EP0197578B1 EP86200430A EP86200430A EP0197578B1 EP 0197578 B1 EP0197578 B1 EP 0197578B1 EP 86200430 A EP86200430 A EP 86200430A EP 86200430 A EP86200430 A EP 86200430A EP 0197578 B1 EP0197578 B1 EP 0197578B1
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EP
European Patent Office
Prior art keywords
alkyl
amine
weight
dispersion according
siloxane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP86200430A
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English (en)
French (fr)
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EP0197578A2 (de
EP0197578A3 (en
Inventor
Axel König
Francesco De Buzzaccarini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Priority claimed from GB858508130A external-priority patent/GB8508130D0/en
Priority claimed from GB858520803A external-priority patent/GB8520803D0/en
Application filed by Procter and Gamble European Technical Center, Procter and Gamble Co filed Critical Procter and Gamble European Technical Center
Priority to AT86200430T priority Critical patent/ATE64752T1/de
Publication of EP0197578A2 publication Critical patent/EP0197578A2/de
Publication of EP0197578A3 publication Critical patent/EP0197578A3/en
Application granted granted Critical
Publication of EP0197578B1 publication Critical patent/EP0197578B1/de
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins

Definitions

  • This invention relates to textile treatment compositions. More particularly it relates to textile treatment compositions suitable for use in the rinse cycle of a textile laundering operation to provide fabric softening/static control benefits, the compositions being characterized by excellent softening, water dispersibility and storage properties after prolonged storage at both elevated and sub-normal temperatures.
  • rinse-added fabric softening compositions contain, as the active component, substantially water-insoluble cationic materials having two long alkyl chains. Typical of such materials are di-hardened tallow dimethylammonium chloride, and imidazolinium compounds substituted with two tallow groups. These materials are normally prepared in the form of a dispersion in water and it is generally not possible to prepare such aqueous dispersions with more than about 10 % of cationic softener without encountering severe product viscosity and storage-stability problems. Although more concentrated dispersions of softener materials can be prepared as described in European Patent Application No.
  • U.S. Patent 4 454 049 issued June 12, 1984 to MacGilp et al discloses concentrated liquid fabric softeners comprising substantial amounts at least 10%, more typically about 30 - 40%, of water miscible organic solvent.
  • U.S. Patent 2 995 520 issued August 8, 1961 to Luvisi et al discloses the use of the acid salts of certain imidazoline derivatives for softening of fibrous materials such as cotton and paper.
  • the treatment baths used for treating textiles contain from 0.001% to 1% of an acid salt of an imidazoline derivative.
  • quaternary ammonium salts are, in the context of fabric softening, preferred over acid salts of, e.g., acyclic tertiary amines or cyclic amines.
  • compositions of the present invention have excellent stability at both elevated and sub-normal temperatures, even under prolonged storage conditions. These compositions further provide excellent softening, anti-static and fabric rewettability characteristics across a broad range of fabric types.
  • the present invention provides a stable aqueous dispersion comprising:
  • compositions of the present invention are based upon the discovery that stable aqueous dispersion can be formulated with certain cyclic amines, even at high amine concentration, and a conventional di(higher alkyl) quaternary ammonium salt, without the use of substantial amounts of organic solvent.
  • the amines used in the compositions of the present invention are selected from the group consisting of compounds of the formula I. wherein n is 2 or 3, preferably 2; R1 and R2 are, independently, a C8-C30 alkyl or alkenyl, preferably c11 , -c22 alkyl, more preferably C15-C18 alkyl, or mixtures of such alkyl radicals. Examples of such mixtures are the alkyl radicals obtained from coconut oil, "soft" (non-hardened) tallow, and hardened tallow.
  • Q is CH, CH2, NH, or N, preferably N.
  • T is NR5, R5 being H or C1-C4 alkyl, preferably H, and R4 is a divalent C1-C3 alkylene group or (C2H4O) m , wherein m is an number of from 1 to 8; or X is R4.
  • compositions of the present invention comprise from 1% to 40% by weight of the amine, preferably from 2% to 35%, and more preferably from 2% to 20%.
  • Detergent carryover tends to negatively affect the softening performance of rinse added softeners. It has been found that the amines of formula I are less sensitive to detergent carryover than, e.g. ditallowdimethylammonium chloride.
  • the dispersions herein contain a conventional di(higher alkyl) quaternary ammonium softening agent.
  • “higher alkyl” as used in the context of the quaternary ammonium salts herein is meant alkyl groups having from 8 to 30 carbon atoms, preferably from 11 to 22 carbon atoms.
  • Examples of such conventional quaternary ammonium salts include (i) acyclic quaternary ammonium salts having the formula: wherein R2 is an acyclic aliphatic C15-C22 hydrocarbon group.
  • R3 is a C1-C4 saturated alkyl or hydroxyalkyl group, R4 is selected from R2 and R3, and A is an anion.
  • R1 is an acyclic aliphatic C15-C21 hydrocarbon group
  • R2 is a divalent alkylene group having 1 to 3 carbon atoms
  • R5 and R8 are C1-C4 saturated alkyl or hydroxyalkyl groups
  • a - is an anion:
  • n is equal to 1 to about 5, and R1, R2, R5 and A - are as defined above ;
  • Component (i) are the well-known dialkyldimethylammoniums salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di(hydrodrogenated tallow) dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride.
  • Component (ii) are methylbis(tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, R5 is a methyl group, R8 is a hydroxyalkyl group and A is a methylsulfate anion; these materials are available from Sherex Chemical Company under the trade names Varisoft (R) 222 and Varisoft (R) 110, respectively.
  • Examples of (iv) are 1-methyl-1-tallowamido-ethyl-2-tallowimidazolinium methylsulfate and 1-methyl-1-(hydrogenated tallowamidoethyl)-methylsulfate.
  • the quaternary ammonium salt (b) preferably comprises from 1% to 20%, more preferably 2% to 20% by weight of the composition herein.
  • the weight ratio amine (a); quaternary ammonium salt (b) is in the range from 3:1 to 1:10, preferably from 3:1 to 1:3.
  • di(higher alkyl)imidazolinium compounds are preferred for use herein, in particular the 1- (lower alkyl)-1-(higher alkyl)amidoethyl-2-(higher alkyl) imidazolinium compounds, wherein “lower alkyl” signifies alkyl having from 1 to 4 carbon atoms, and “higher alkyl” signifies alkyl having from 11 to 22 carbon atoms.
  • the dispersion further comprises Bronstedt acids having a pKa value of 6 or less.
  • the amount of acid should be such that the pH of the dispersion, after mixing, is not greater than 5, preferably not greater than 4, and most preferably in the range of from 2.5 - 4.
  • the amount of acid is from 1% to 50% by weight of the amine, preferably from 2% to 30%, most preferably from 3 to 15%.
  • suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C1-C5) carboxylic acids, aromatic carboxylic acids, like benzoic acid, and alkylsulfonic acids.
  • Suitable ionorganic acids include HCl, HBr, H2SO4, HNO3 and H3PO4.
  • Suitable organic acids include benzoic acid, formic, acetic, methylsulfonic and ethylsulfonic acid.
  • Preferred acids are phosphoric, formic and methylsulfonic acid.
  • compositions of the present invention can be formulated without the use of any organic solvent.
  • organic solvents for example, low molecular weight, water miscible aliphatic alcohols, does not harm the storage stability, the viscosity, or the softening performance of the compositions of this invention.
  • the amine will be obtained from a supplier of bulk chemicals in solid form of as a solution in an organic solvent, e.g. isopropanol. There is no need, whatsoever, to remove such a solvent in making the compositions of this invention. Indeed, additional solvent may be added, if this is deemed desirable.
  • organic solvent e.g. isopropanol
  • organic solvents are expensive, and difficult to handle because of their flammability and, sometimes, toxicity. It is therefore desirable to formulate the present compositions with low levels of organic solvent, i.e., less than 10%, preferably less than 2%.
  • compositions herein can optionally contain an aqueous emulsion of a predominantly linear polydialkyl or alkyl, aryl siloxane in which the alkyl groups can have from one to five carbon atoms and may be wholly or partially fluorinated.
  • Suitable silicones are polydimethyl siloxanes having a viscosity at 25°C in the range from 100 to 100,000 centistokes (mm2/s) preferably in the range from 300 to 6,000 centistokes (mm2/s).
  • Silicones having cationic character show an enhanced tendency to deposit. Silicones found to be of value in providing fabric feel benefits have a predominantly linear character and are preferably polydialkyl siloxanes in which the alkyl group is most commonly methyl. Such silicone polymers are frequently manufactured commercially by emulsion polymerisation using a strong acid or strong alkali catalyst in the presence of a nonionic or mixed nonionic-anionic emulsifier system.
  • the optional silicone component embraces a silicone of cationic character which is defined as being one of
  • silicone component suitable for use herein are more fully disclosed in British Patent No. 1.549.180.
  • compositions optionally contain nonionics as have been disclosed for use in softener compositions.
  • nonionics and their usage levels, have been disclosed in U.S. Patent 4.454.049, issued June 12,1984 to Mac Gilp et al.
  • nonionics suitable for the compositions herein include glycerol esters (e.g., glycerol monostearate), fatty alcohols (e.g.,stearyl alcohol), and alkoxylated fatty alcohols.
  • glycerol esters e.g., glycerol monostearate
  • fatty alcohols e.g.,stearyl alcohol
  • alkoxylated fatty alcohols e.g., stearyl alcohol
  • the nonionics, if used, are typically used at a level in the range of from 0.5 - 10% by weight of the composition.
  • these compositions can contain relatively small amounts of electrolyte.
  • a highly preferred electrolyte is CaCl2. It has been found that the Brookfield viscosities of highly concentrated dispersions can be reduced to less than 100 cps,(100 mPas) using relatively small amounts of CaCl2 (e.g., 600 ppm).
  • compositions herein can optionally contain other ingredients known to be suitable for use in textile softeners.
  • adjuvants include perfumes, preservatives, germicides, colorants, dyes, fungicides, stabilizers, brighteners and opacifiers. These adjuvants, if used, are normally added at their conventional levels. However, in the case of composition ingredients utilized for a fabric treatment effect, e.g., perfumes, these materials can be added at higher than normal levels, corresponding to the degree of concentration of the product.
  • compositions are prepared :

Claims (7)

  1. Stabile wäßrige Dispersion, umfassend:
    (a) 1 Gew.-% bis 40 Gew.-% an einem Amin, welches aus der Gruppe bestehend aus den cyclischen Aminen der Formel:
    Figure imgb0012
     worin n 2 oder 3 beträgt, R₁ und R₂ unabhängig voneinander einen C₈-C₃₀-Alkyl- oder -Alkenylrest darstellen, Q für CH, CH₂, NH oder N steht, x für
    Figure imgb0013
     steht, worin T NR₅ bedeutet, wobei R₅ H oder C₁-C₄-Alkyl darstellt, und R₄ eine zweiwertige C₁-C₃-Alkylengruppe oder (C₂H₄O)m ist, worin m eine Zahl von 1 bis 8 darstellt; oder X R₄ bedeutet; und Gemischen hievon, ausgewählt ist;
    (b) eine Verbindung, ausgewählt aus der Gruppe von herkömmlichen Weichmachern auf der Basis von quaternären Ammoniumsalzen, welche zwei Alkylgruppen besitzen, wovon jede 8 bis 30 Kohlenstoffatome aufweist, wobei das Gewichtsverhältnis von (a) zu (b) im Bereich von 3:1 bis 1:10 beträgt; und
    (c) 1 Gew.-% bis 50 Gew.-% von dem Amin eines Dispersionshilfsmittels, welches aus der Gruppe von Bronstedt-Säuren mit einem pKa-Wert von nicht mehr als 6 ausgewählt ist; mit der Maßgabe, daß der pH-Wert der Dispersion nicht mehr als 5 beträgt.
  2. Dispersion nach Anspruch 1, worin das Gewichtsverhältnis (a):(b) im Bereich von 3:1 bis 1:3 liegt.
  3. Dispersion nach einem der vorherstehenden Ansprüche, welche 2 Gew.-% bis 35 Gew.-% des Amins umfaßt.
  4. Dispersion nach einem der vorherstehenden Ansprüche, worin das Amin ein 1-(C11-22-Alkyl)amidoethyl-2-(C11-22-alkyl)imidazolin ist.
  5. Dispersion nach einem der vorherstehenden Ansprüche, welche ferner eine Emulsion aus überwiegend linearem Di(C₁-C₅)alkyl- oder C₁-C₅-Alkyl-arylsiloxan umfaßt, worin die Alkylgruppen teilweise oder vollständig fluoriert sein können und welche mit kationischen Stickstoffgruppen substituiert sein können, wobei das Siloxan eine Viskosität bei 25°C von mindestens 100 Centistokes (mm²/s) und bis zu 100.000 Centistokes (mm²/s) besitzt; wobei das Gewichtsverhältnis von Siloxangehalt der Emulsion zur Aminkomponente im Bereich von 5:1 bis 1:100, vorzugsweise 2:1 bis 1:10 liegt.
  6. Dispersion nach Anspruch 6, worin das Siloxan ein Polydimethylsiloxan ist.
  7. Dispersion nach einem der vorherstehenden Ansprüche, welche ferner 0,5 Gew.-% bis 10 Gew.-% von einem nichtionischen Mittel, vorzugsweise einem Glycerinester, einem Fettalkohol oder einem alkoxylierten Fettalkohol umfaßt.
EP86200430A 1985-03-28 1986-03-19 Mittel zum Behandeln von Textilien Expired - Lifetime EP0197578B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86200430T ATE64752T1 (de) 1985-03-28 1986-03-19 Mittel zum behandeln von textilien.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB858508130A GB8508130D0 (en) 1985-03-28 1985-03-28 Textile treatment composition
GB8508130 1985-03-28
GB858520803A GB8520803D0 (en) 1985-08-20 1985-08-20 Textile treatment compositions
GB8520803 1985-08-20

Publications (3)

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EP0197578A2 EP0197578A2 (de) 1986-10-15
EP0197578A3 EP0197578A3 (en) 1987-12-02
EP0197578B1 true EP0197578B1 (de) 1991-06-26

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Country Status (17)

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EP (1) EP0197578B1 (de)
JP (1) JPH0768668B2 (de)
KR (1) KR930008698B1 (de)
CN (1) CN1005735B (de)
AU (1) AU591108B2 (de)
CA (1) CA1279447C (de)
DE (1) DE3679927D1 (de)
DK (1) DK139886A (de)
EG (1) EG17723A (de)
FI (1) FI861341A (de)
GB (1) GB2174422B (de)
HK (1) HK103892A (de)
IE (1) IE59115B1 (de)
MA (1) MA20655A1 (de)
MX (1) MX165248B (de)
MY (1) MY100080A (de)
TR (1) TR23492A (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8508129D0 (en) * 1985-03-28 1985-05-01 Procter & Gamble Ltd Textile treatment composition
US4668234A (en) * 1985-08-15 1987-05-26 E. I. Du Pont De Nemours And Company Aromatic polyamide fibers and process for stabilizing such fibers with surfactants
US4661267A (en) * 1985-10-18 1987-04-28 The Procter & Gamble Company Fabric softener composition
GB2188653A (en) * 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
DE3720331A1 (de) * 1987-06-19 1988-12-29 Huels Chemische Werke Ag Konzentrierte waescheweichspuelmittel
EP0316996A3 (de) * 1987-11-18 1990-04-04 The Procter & Gamble Company Verfahren zur Herstellung von Textilbehandlungsmitteln
EP0345842A3 (de) * 1988-05-27 1990-04-11 The Procter & Gamble Company Wäscheweichspülerzusammensetzungen, die Mischungen substituierter Imidazolinester und quaternärer Esterammoniumsalze enthalten
US5254269A (en) * 1991-11-26 1993-10-19 Lever Brothers Company, Division Of Conopco, Inc. Fabric conditioning composition containing an emulsified silicone mixture
US5723426A (en) † 1996-02-29 1998-03-03 Zhen; Yueqian Liquid laundry detergent compositions containing surfactants and silicone emulsions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995520A (en) * 1956-06-11 1961-08-08 Nalco Chemical Co Treatment of fibrous materials and compositions therefor
FR2391312A1 (fr) * 1977-05-16 1978-12-15 Basf Ag Plastifiant textile aqueux liquide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7609621A (nl) * 1975-09-04 1977-03-08 Hoechst Ag Textielbehandelingsmiddel.
EP0056695B2 (de) * 1981-01-16 1987-09-09 THE PROCTER & GAMBLE COMPANY Textilbehandlungsmittel
GB8508129D0 (en) * 1985-03-28 1985-05-01 Procter & Gamble Ltd Textile treatment composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995520A (en) * 1956-06-11 1961-08-08 Nalco Chemical Co Treatment of fibrous materials and compositions therefor
FR2391312A1 (fr) * 1977-05-16 1978-12-15 Basf Ag Plastifiant textile aqueux liquide

Also Published As

Publication number Publication date
EG17723A (en) 1990-10-30
GB8607691D0 (en) 1986-04-30
AU591108B2 (en) 1989-11-30
DE3679927D1 (de) 1991-08-01
DK139886A (da) 1986-09-29
IE860831L (en) 1986-09-28
EP0197578A2 (de) 1986-10-15
FI861341A0 (fi) 1986-03-27
MX165248B (es) 1992-11-04
TR23492A (tr) 1990-02-01
JPS61275473A (ja) 1986-12-05
MA20655A1 (fr) 1986-10-01
EP0197578A3 (en) 1987-12-02
HK103892A (en) 1992-12-31
CN86102993A (zh) 1986-10-01
MY100080A (en) 1989-08-18
GB2174422A (en) 1986-11-05
JPH0768668B2 (ja) 1995-07-26
CN1005735B (zh) 1989-11-08
IE59115B1 (en) 1994-01-12
AU5535386A (en) 1986-10-02
FI861341A (fi) 1986-09-29
GB2174422B (en) 1989-01-11
DK139886D0 (da) 1986-03-25
KR930008698B1 (ko) 1993-09-13
CA1279447C (en) 1991-01-29
KR860007415A (ko) 1986-10-13

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